Patent GB-987320-A (GB)
Title: Coordination polymers having a backbone containing trivalent octahedral metal atoms
IPC: C07F5/06
Filed: 1963-03-08
Abstract: The invention comprises co-ordination polymers whose molecule contains a doubly bridged trivalent octahedral metal co-ordinated with a bidentate ligand, the polymers having a repeating unit of structure:- <FORM:0987320/C2/1> where M is the trivalent octahedral metal, AB is a bidentate ligand of charge - 1 (i.e. a negative monovalent ion), and X1 and X2 are the same or different bridging group, being the anions of acids, also of charge - 1.  M may be any metal characterized by a co-ordination number of 6 in the 3 + oxidation state (e.g. Cr, Co, Ru, In, Rh, Ir, Ga, Al, Tl, Fe).  AB is any anion of charge - 1 capable of forming an essentially strain-free (i.e. five- or six-membered) ring with M, by co-ordination of two covalent bonds formed through two groups of AB, one of which provides a valence of - 1.  This liquid may be represented by:- <FORM:0987320/C2/2> wherein A is a neutral donor group (e.g. keto oxygen or amino), B is a group of charge  - 1 formed by removal of a proton from a group such as -OH or -NH2, and F-G-(H) is composed of groups such as <FORM:0987320/C2/3> <FORM:0987320/C2/4> Specific ligands include the anions derived from acetyl acetone, alanine, glycine, picolinic acid, benzoyl acetone, biguanidine, ethylacetoacetate, phenyl biguanidine, and 8-quinolinol.  The bridging groups X1 and X2 preferably comprise anions of an acid R2M1(Y)YH, wherein M1 is a Group VB element of atomic number greater than 7 (i.e. P, As, Sb, Bi) and Y is oxygen or sulphur, especially preferred bridging groups being phosphinic acids.  R may be any organic group which is inert under the conditions in which the polymers are prepared, such as alkyl, aryl, alkoxy or aryloxy, or a similarly inert inorganic group, such as -NH2.  Other acid anions of charge - 1, such as those derived from organic carboxylic acids, may be used, providing they furnish two donor sites so related that the ion must act as a catenating group, e.g. <FORM:0987320/C2/5> where R is an alkyl or aryl group of from 1 to 10 carbon atoms. The polymers may be prepared by the following general methods, and are obtained as mixtures of polymers of various molecular weights which may to some extent be fractionated by virtue of the differing solubilities of the high and low molecular weight polymers in organic solvents such as ether, CHCl3, and benzene.  Polymers of above about 20 polymeric units per molecule (see Division C3) are, in general, insoluble in such solvents. Preparation procedures are as follows:-(1) The metal chelate M(AB)3 and the acid HX1, or acids HX1 and HX2, where AB, M, X1 and X2 are as designated above, may be heated together in molar ratio of 1 : 2 in an inert atmosphere (e.g. nitrogen or argon), at a temperature sufficient to volatilize HAB, until no further HAB is evolved.  Higher temperatures tend to produce higher molecular weight products; (2) the reactants M(AB)3 and HX1 and HX2 may be heated in a liquid of high boiling point (e.g. biphenyl or chlorinated biphenyls), and volatile by-products are distilled out of the reaction system.  The polymer may then be separated from the liquid by decantation, filtration, or centrifugation; (3) the above methods may be employed using the lowest members of the polymer series (i.e. [M(AB)2X1X2]2), in place of M(AB)3, as reactants; (4) the conversion of one ligand group in the polymer to another may be effected by reacting the polymer, either by fusion, or heating in a high boiling point liquid, as in (2), with the protonated form of a less volatile ligand.  This causes the displacement of the original ligand from the polymer by the less volatile one; (5) higher molecular weight polymers may be prepared from the dimer form [M(AB)2X1X2]2, by maintaining it at a temperature sufficient to volatilize M(AB)3, until constant weight is achieved; (6) mixed metal ligands, of the type M(AB)(A1B1)2 or M(AB)a2b2, where A1B1 is a bidentate ligand more volatile in the protonated state than AB, a is a neutral unidentate ligand (e.g. pyridine), and b is an anion (e.g. chloride), may be reacted with HX1 and HX2, either by fusion or heating in an inert solvent (e.g. CHCl3).  The choice of method and reactant should be governed by the nature of the reactants.  Low temperature reaction in a solvent rather than by fusion, is desirable for cobalt chelates as cobalt tends to change its valency state at high temperatures. Ferric iron chelates tend to react with diphenyl phosphinic acids to give iron phosphinates, and other bridging groups, such as methyl phosphinic acid or benzoic acid are here preferred.  The polymers are solids which decompose at about 300 DEG  C. or above.  They may be used as pigments, as many of them are coloured, and also may be employed in situations where retention of elasticity and strength at high temperatures will be desirable, such as in gaskets, O-rings, and protective coatings.ALSO:The invention comprises co-ordination polymers involving a doubly bridged trivalent octahedral metal co-ordinated with a bidentate ligand, having a repeating unit of structure: <FORM:0987320/C3/1> where M is the metal, AB is bidentate ligand of charge -1 (i.e. a negative monovalent ion), and X1 and X2 are acid ions of charge -1.  M may be any metal characterized by a co-ordination number of 6 in the 3 + oxidation state (e.g. Cr, Co, Ru, In, Rh, Ir, Ga, Al, Tl, Fe).  AB is any anion of charge -1 capable of forming an essentially strain-free ring (i.e. five or six membered), with the metal M, by co-ordination of two covalent bonds formed through two groups of AB, one of which provides a valence of -1. This ligand may be represented: <FORM:0987320/C3/2> wherein A is a neutral donor group (e.g. keto oxygen, or amino), B is a group of charge -1, formed by removal of a proton from a group such as -OH1 or -NH2, and F-G-(H)- is composed of groups such as: <FORM:0987320/C3/3> ; <FORM:0987320/C3/4> ; <FORM:0987320/C3/5> ; <FORM:0987320/C3/6> ; or <FORM:0987320/C3/7> Specific compounds which may be used as ligands include the anions derived from:  acetyl acetone;  alanine; glycine; picolinic acid; benzoyl acetone;  biguanidine; ethyl acetoacetate;  8 guinolinol; and phenyl biguanidine.  The bridging groups, X1 and X2, comprise the anions of an acid, preferably of structure R2M1Y(YH) based on Group VB elements of atomic number greater than 7 as M1; (i.e. P, As, Sb, Bi), with Y as oxygen or sulphur.  Y is preferably oxygen, M preferably phosphorus, thus making the preferred bridging groups to be phosphinic acids.  R may be any organic group which is inert under the conditions in which the polymers are prepared (e.g. alkyl, aryl, alkoxy, or aryloxy), or a similarly inert inorganic group such as -NH2.  Other acid anions of charge -1, such as organic carboxylic acids, may be used, providing that they furnish two donor sites so related that the ion must act as a catenating group (e.g. R-COO-, where R is alkyl or aryl, preferably C1-C10 hydrocarbon). The polymers may be prepared by the following general methods, being obtained as mixtures of various polymers ranging from dimers to polymers of over 20 polymeric units:  (1) Reaction of the metal chelate M(AB)3 with the bridging group acid or acids at elevated temperature; (2) reaction of the dimer [M(AB)2 X1X2]2 with the bridging group acid or acids at elevated temperature; (3) exchange of one ligand group for another in the polymer by reaction of the polymer with the protonated form of a different ligand, at elevated temperature; (4) action of heat on the dimer [M(AB)2 X1X2]2; (5) reaction of a mixed metal ligand, M(AB)(A1B1)2, where A1B1 is more volatile than AB, or of the type MABa2b2, where a is a unidentate ligand and b is an anion, with acid or acids that will form a bridging group, at elevated temperature.  The polymers are solids decomposing at Ca. 300 DEG  C. or above; they may be used as pigments, if coloured, or in circumstances where retention of elasticity and strength at high temperature is desirable.